High molecular weight thermoplastic aromatic sulfoxy polycarbonates



2,999,846 HIGH MOLECULAR WEIGHT THERMOPLASTIC AROMATIC SULFOXYPOLYCAONATES Hermann chnell, Krefeld-Urdingen, and Heinrich Krimm,Krefeid-Bockum, Germany N Drawing. Filed Nov. 27, 1957, Ser. No. 699,194Claims priority, application Germany Nov. 30, 1956 9 Claims. (Cl.260-49) The present invention is concerned with a process for theproduction of high molecular weight thermoplastic materials.

The subject of the US. patent application Serial No. 572,793 is aprocess for the production of high molecular weight thermoplasticmaterials, which comprises converting dihydroxy-diarylene-sulphonesalone, or together with other dihydroxy compounds into high molecularweight polycarbonates.

The present invention is a further development of this process. Theobjects of the present invention are new thermoplastic materials of thepolyester type, melting at high temperatures without decomposition andhaving technically useful properties. The new polycarbonates arecharacterized by the essential recurring of units consisting of residuesof dihydroXy-diarylene sulphoxides selected from the group consisting ofunsubstituted dihydroxyarylene sulphoxides and dihydroxy-diarylenesulphoxides with aliphatic side chains up to 4 carbon atoms at thearomatic rings.

They include as the essential recurring unit a unit of the formula:

0 O 1)n ion in which R is the dioxy radical of dihydroxy compound, A andB are the same or different aromatic groups selected from the groupconsisting of the benzene and the naphthalene ring, R and R arealiphatic substituents containing up to 4 carbon atoms and n is 0 to 4.

The further object of the invention is a process for producing such newpolycarbonates containing residues of dihydroxy-diarylene sulphoxides.

The new plastic materials show but a slight tendency to crystallizationand are soluble in a large number of organic solvents and solventmixtures such as methylene chloride, chloroform, cyclo-hexanone,dimethyl formamide, dioxane and phenol. They can be Worked up to films,foils or lacquer coatings from such solutions. Since they generally meltat temperatures above 200 C. without decomposition, they may also beWorked up, for example, by compression moulding, injection moulding,flame spraying, or by the spin sinter process to give useful mouldedobjects or hard coatings which adhere tenaciously.

In the dihydroxy-diarylene sulphoxides used for forming thepolycarbonates according to the invention, the arylene residues can bethe same or different. The arylene residues can furthermore carryhydrogen atoms or substituents which are incapable of taking part in thereaction to polycarbonates, e.g. alkyl groups such as ethyl, methyl,propyl or tertiary butyl.

As examples of dihydroxydiarylene sulphoxides of the specified type, thefollowing may be mentioned:

4,4-dihydroxy-diphenylene sulphoxide, 2,2'-dihydroxy-diphenylenesulphoxide, 3,3'-dihydroxy-diphenylene sulphoxide,4,4-dihydroxy-2,2-dimethyl-diphenylene sulphoxide,4,4'-dihydroxy-3,3-dirnethyl-diphenylene sulphoxide,2,2-dihydroxy-4,4-dimethyl-diphenylene sulphoxide,

Patented Sept. 12, 1961 2 4,4'-dihydroXy-2,2'-diethyl-diphenylenesulphoxide, 4,4'-dihydroxy-3,3 -diethy1-diphenylenesulphoxide,4,4-dihydroxy-2,2'-di-tert.butyl-diphenylene sulphoxide,4,4'-dihydroxy-3,3-di-tert.-buty1 diphenylene sulphoxide and2,2-dihydroxy-1,1-dinaphthalene sulphoxide.

We prefer the 4,4-dihydroxy-diphenylene sulphoxides, mentioned above.They are, for example, easily obtained by condensation of thionylchloride with the corresponding phenols in the presence ofFriedel-Crafts catalysts.

As examples of the other dihydroxy compounds which may be used inadmixture with the dihydroxy-diarylene sulphoxides, if desired, theremay be mentioned the following: aliphatic dihydroxy compounds, such as:ethylene glycol, diethylene glycol, triethylene glycol, polyethyleneglycol, the corresponding thioethers, dior polyglycols obtained frompropylene oxide-1,2, propanediol-1,2, propanediol-1,3, butanedio1-1,3,butanediol-1,4, Z-methylpropanediol-l, 3, pentanediol-1,5,2-methylpropanediol-1,3, hexanedio1-1,6, octanediol-1,8,2-ethylhexanediol 1,3, decanediol-1,10, and o-, por m-xylenene glycol;cycloaliph-atic dihydroxy compounds, such as cyclo-hexanediol- 1,2,cyclohexanediol 1,4, 2,2-(4,4'-dihydroxy-dicyclo hexyl)-propane and2,6-dihydroxy-decahydronaphthalene; and aromatic dihydroxy compounds,such as hydroquinone, resorcinol, pyrocatechol, 4,4'-dihydroxy-diphenyl,2,2-di-hydroxy-diphenyl, 1,4-dihydroxy-naphthalene, 1,6-dihydroxy-naphthalene, 2,6 dihydroxy-naphthalene, 1,2-dihydroxy-naphthalene, 1,5-dihydroxy-anthracene,2,2-dihydroxy-dinaphthalene-l,1', and 0-, m-, or p-hydroxybenzylalcohol,and especially di-monohydroxy-arylene alkanes, such as4,4-dihydroXy-diphenylene-methane,

1,1-(4,4'-dihydroxy-diphenylene) -ethane,

1,1-(4,4'-dihydroxy-diphenylene)-propane,

l,1(4,4dihydroxy-diphenylene) -butane,

1, 1- (4,4'-dihydroxy-diphenylene) -2-rnethyl-propane,

1,1 (4,4-dihydroxy-diphenylene) -heptane,

1, 1-( 4,4'-dihydroxy-diphenylene) -1-phenyl-methane,

( 4,4'dihydroxy-diphenylene) 4-methylphenylene) methane,

(4,4'-dihydroxy-diphenylene) -(4-ethy1-pheny1ene) methane,

(4,4-dihydroxy-dipheny1ene)-(4-isopropyl methane,

(4,4-dihydroxy-diphenylene) 4-butyl-phenylene) methane,

( 4,4'-dihydroxy-diphenylene) -benzy1-methane,

(4,4'-dihydroxy-diphenylene) -m-furyl-rnethane,

2,2- 4,4'-dihydroxy-diphenylene) -prop ane,

2,2- (4,4-dihydroxy-dipheny1ene) -butane,

2,2-(4,4'-dihydroxy-diphenylene)-pentane (melting point 2,2-4,4'-dihydroxy-diphenylene) -4-methyl-pentane,

2,2-(4,4-dihydroxy-diphenylene)-heptane (boiling point 198-200 C. under0.3 mm. mercury gauge),

2,2- 4,4-dihydroxy-diphenylene) -octane,

2,2-(4f-dihydroxy-diphenylene) -nonane (melting point 1, 1-(4,4'-dihydroxy-diphenylene) -1-phenyl-ethane,

(4,4-dihydroxy-diphenylene) -1-(a-furyl) -ethane,

3,3 4,4-dihydroxy-diphenylene) -pentane,

4,4 4,4'-dihydroxy-diphenylene) -heptane,

1,1-(4,4-dihydroxy-diphenylene) -cyclopentane,

1,1-(4,4'-dihydroxy-diphenylene)-cyclohexane,

2,2-(4,4'-dihydroxy-diphenylene) decahydronaphthalene (melting point 181C.),

2,2-(4,4'-dihydroxy-3,3'-dicyclohexyl-diphenylene) propane (meltingpoint 144-146 C.),

2,2-(4,4'-dihydroxy-3 methyl diphenylene) (melting point 114 C.),

phenylene) propane l,l(4,4'-dihydroxy-3,3'-dimethyl6,6di-tert.butyldiphenylene) -1-pheny1-methane,

1,l(4,4'-dihydroxy-3,3-dirnethyl 6,6'-di-tert.butyldiphenylene)-2-methyl-2-p entane,

1,1-(4,4'-dihydroxy-3,3'-dimethyl 6,6-di-tert.butyldiphenylene)-2-ethyl-2-hexane, and 1,l-(4,4-dihydroxy-3,3'-dimethyl6,6'-di-tert.amyl diphenylene)-butane, furthermore4,4-dihydroxy-diphenylene sulphone, 2,2'-dihydroxy-d-iphenylenesulphone, 3,3'-dihydroxy-diphenylene sulphone,4,4-dihydroxy-2,2'-dimethyl-diphenylene sulphone,4,4'-dihydroxy-3,3'-diethyl-diphenylene sulphone,2,2'-dihydroxy-4,4-dimethyl-diphenylene sulphone,4,4-dihydroxy-Z,2'-diethyl-diphenylene sulphone,4,4'-dihydroxyl-3,3'-die-thyl-diphenylene sulphone,4,4'-dihydroxy-2,2-di-tert.butyl-diphenylene sulphoue,4,4-dihydroxy-3,3'-di-tert.butyl-diphenylene sulphone and2,2'-dihydroxy-1, l '-dinaphthylene sulphone.

The process according to the present invention for producing the newpolycarbonates consists in reacting said dihydroxy-diarylenesulphoxides, or mixtures thereof with the aforementioned dihydroxycompounds with derivatives of carbonic acid selected from the groupconsisting of diesters of carbonic acid, especially diarylesters, mixeddiesters of the aforesaid dihydroxy-diarylene sulphoxides and otherdihydroxy compounds, phosgene, and bis-chlorocarbonic acid esters of theaforesaid di-hydroxy-diarylene sulphoxides and of the other dihydroxycompounds.

Thus it is possible to produce the new polycarbonates byinteresterifying dihydroxy-diarylene sulphoxides, optionally mixed withthe aforesaid dihydroxy compounds and suitably in the presence of acidicor basic catalysts, with dialkyl, dicycloalkyl, or diaryl carbonates,such as dimethyl-, -diethyl-, dipropyl-, dibutyl-, diamyl-, dioctyl-,dicyclohexyl-, and especially with the diphenyland di-o-, mor p-toluylcarbonate, or with the mixed esters, for instance with the methyl-ethyl,the methyl-propyl, the ethylpropyl, the methyl-cyclohexyl, theethyl-cyclohexyl, the propyl-cyclohexyl, the methyl-phenyl, theethyl-phenyl, the propyl-phenyl, the ethyl-o-, mor p-toluyl and thecyclohexyl-phenyl carbonate, also with mixed biscarbonates ofmonohydroxy compounds mentioned above and the aforesaiddihydroxy-diarylene sulphoxid'es of the type: bis-(arylor cycloalkyloralkyl-carbonato-arylene)-sulphox-ide, particularly at elevatedtemperatures from about 50-330 C. and especially from about 120 to about290 C. and under reduced pressure for instance up to 0.1 mm. mercurygauge.

By re-esterifying the mentioned carbonic acid diesters, thecorresponding alkyl or cycloalkyl alcohols or the corresponding phenolsare split off.

The re-esterifying process has to be carried out while excluding oxygen.We prefer to pass an inert-gas such as hydrogen, nitrogen, or carbondioxide gas through the melt.

The re-esterification may be activated by re-esterifying catalysts, suchas inorganic bases, for example caustic soda and potassium hydroxide,high boiling organic bases such as acridine, metal hydrides such aslithium and calcium hydride, alkali or alkaline earth metals such assodium, potassium, magnesium, and calcium, metal oxides such as zincoxide, aluminium oxide, lead oxide, antimonotrioxide, cerium oxide, andboron oxide, acids such as phosphoric acid and p-toluene sulphonic acid,salts such as sodium benzoate, calcium acetate, and boron phosphate, andalcoholates and phenolates.

The new polycarbonates can also be produced by introducing phosgene intosolutions of dihydroxy-diarylene sulphoxides, eventually in mixture withthe aforesaid dihydroxy compounds in organic bases such asdimethylaniline, diethylaniline, trimethylamine, and pyridine, or inindifierent organic solvents, such as petrol, ligroin, cyclohexane,methylcyclohexane, benzene, toluene, xylene, chloroform, methylenechloride, carbon tetrachloride, trichloroethylene, di-chloroethane,methylacetate, and ethylacetate, with addition of an acid-binding agent,e.g tertiary amines.

A process particularly suitable for producing polycarbonates consists inintroducing phosgene into the aqueous solution or suspension of alkalior alkaline earth metal salts, such as lithium, sodium, potassium, andcalcium salts of the dihydroxy-diarylene sulphoxides or mixturescontaining them, preferably in the presence of an excess of a base, suchas lithium, sodium, potassium and calcium hydroxide or carbonate. Thepolycarbonates then precipitate out from the aqueous solution.

The conversion in the aqueous solution is promoted by the addition ofreaction inert solvents of the kind mentioned above which are capable ofdissolving phosgene and eventually the produced polycarbonate.

The phosgene may be used in an equivalent amount. Generally, however, itis preferable to use an excess of the phosgene. Suitable temperaturesare from about 0 C. to about 0.

Finally it is also possible to react bis-chlorocarbonates ofdihydroxy-diarylene sulphoxide, optionally mixed with such of theaforementioned other dihydroxy compounds, or with the aforementioneddihydroxy compounds, optionally also with mixtures of such dihydroxycompounds and with dihydroxy-diarylene sulphoxides. The condensationproceeds suitably in the presence of inert solvents and acid-bindingmaterials, e.g. tertiary amines.

When using phosgene or bis-chloroearbonic acid esters as derivatives ofthe carbonic acid in producing polycarbonates according to the inventioncatalysts also may be advantageous. Such catalysts are for instancetertiary or quaternary organic bases or salts thereof, such astrimethylarnine, triethylamine, dimethylaniline, diethylaniline,dimethylcyclohexylamine, and pyridine, or for instance the correspondinghydrochlorides, and tetramethylammoniumhydroxide,triethyloctadecyl-ammoniumchloride, trimethyl-benzylammoniumfluoride,triethylbenzylammoniumchloride, dimethyldodecyl-ammoniumchloride,dimethylbenzylphenyl-ammoniumchloride,trimethylcyclohexylammoniumbromide, and N-methylpyridiniumchloride, inamounts from about 0.05 to about 5 percent by weight. These compoundsmay be added to the reaction mixture before or during the reaction.

Further in some of these cases we prefer to add surface active agents,such as alkali metal salts of higher fatty acids or of sulphom'c acidsof higher aliphatic or of aromatic hydrocarbons and polyoxyethylatedalcohols and phenols. Greater amounts of the quaternary ammonium basesmentioned above, too, act as such surface active agents.

In the production of polycarbonates according to the various processesit further is advantageous to employ small amounts of reducing agents,for example sodium or potassium sulphide, sulphite, and dithionite, orfree phenol and p-tert.butyl-phenol.

By adding monofunctional compounds which are capable of reacting withphosgene or with the end groups of the polycarbonates consisting of thechlorocarbonic acid ester group and which terminate the chains, such asthe phenols, for instance phenol, tert.buty1phenol, cyclohexylphenol,and 2,2-(4-hydroxyphenylene-4'-methoxypheny1ene)propane, as well asaniline and methylaniline, it is possible to regulate the molecularweight of the polycarbonates in wide limits.

For a better understanding of the invention, the following examples aregiven by way of illustration:

Example 1 Into a solution of 234 grams (1 mol) of4,4'-dihydroxydiphenylene-sulphoxide in 1640 grams of 10 percent sodiumhydroxide solution is passed at 20-25 C. after the addition of 1 litreof methylene chloride, 149 grams (1.5 mol) of phosgene. 0.5 gram oftriethylamine and 4 grams of sodium isopropylnaphthalene-sulphonate arethen added and the initially fluid reaction mixture allowed to stiffento a thick paste. This paste is washed out in a kneader with water,dilute hydrochloric acid and again with water, and is then broken up anddried. IA colourless, elastic material with a softening range of 230 to250 C. is obtained which is, for example, soluble in methylene chloride,chloroform, cyclohexanone, dimethyl formamide and phenol. It is suitablefor the production of lacquer coatings and foils from solutions, as wellas for thermoplastic working up to give all types of moulded bodies.

Example 2 Into a solution of 1'17 grams (0.5 mol) of4,4-dihydroxy-diphenylene-sulphoxide and 114 grams (0.5 mol) of 2,2-(4,4-dihydroxy-diphenylene)-propa.ne in 1640 grams of percent sodiumhydroxide solution, is passed at 20-25 C., after the addition of 600grams of methylene chloride, 149 grams (1.5 mols) of phosgene within aperiod of 2 hours. 0.5 gram of triethylamine and 4 grams of sodiumisopropyl naphthalene sulphonate are then added whereupon a sticky pasteis formed. This is washed out in a kneader with water, dilutehydrochloric acid and again with water, and is then broken up and dried.A colourless, elastic material with a softening range of 230 to 250 C.is obtained which is soluble in, for example, methylene chloride,chloroform, cyclohexanone, dimethyl formamide, phenol and dioxane. It issuitable for the production of lacquer coatings and foils fromsolutions, as well as for thermoplastic working up to give mouldedbodies of all types.

We claim:

1. A film-forming high molecular weight resinous thermoplastic linearpolycarbonate of a dihydroxy compound having the formula in which A andB are aromatic radicals selected from the class consisting of benzeneand naphthalene radicals, R and R are alkyl substituents containing upto four carbon atoms, and each n is a number from 0 to 4 inclusive, eachhydroxyl group of said dihydroxy compound being esterified with carbonicacid, thus forming long polycarbonate molecular chains.

2. Products according to claim -1 wherein A and B are the same.

3. Products according to claim 1 wherein the dihydroxy compound is a4,4-dioXy-(diarylene)-sulphoxide.

4. The combination of claim 1 in which each n is zero.

'5. The combination of claim 3 in which the dihydroxy compound is4,4'-dihydroxy diphenylene sulphoxide.

6. A film-forming high molecular weight resinous thermoplastic linearpolycarbonate consisting of the repeating units wherein R is a divalenthydrocarbon radical, A and B are aromatic radicals selected from theclass consisting of benzene and naphthalene radicals, R and R are alkylsubstituents containing up to four carbon atoms, and each n is a numberfrom *0 to 4 inclusive.

'7. Products according to claim 6 wherein R is a diarylene-alkane andthe oXygens by which it is bound are connected to the respective arylenerings of said diarylene-alkane.

8. The combination of claim 7 in which R is 2,2-diphenyl propane, theoxygens by which R is bound are connected to the para positions on therespective phenyl rings, and each n is zero.

9. The combination of claim '6 in which each n is zero.

References Cited in the file of this patent UNITED STATES PATENTS2,455,653 Bralley et al. Dec. 7, 1948 2,799,666 Caldwell July 16, 1957FOREIGN PATENTS 546,375 Belgium Mar. 23, 1956

1. A FILM-FORMING HIGH MOLECULAR WEIGHT RESINOUS THERMOPLASTIC LINEARPOLYCARBONATE OF A DIHYDROXY COMPOUND HAVING THE FORMULA